Process for breaking petroleum emulsions



United States Patent PROCESS FOR BREAKING PETROLEUM EMULSIONS Melvin De Groote, University City, Mo assignor to Petrolite Corporation, Wilmington, Del, a corporation of Delaware No Drawing. Application September 19, 1952,

Serial No. 310,552

32 Claims. ((1252-34 1) This invention relates to processesor procedures .particularly adapted for preventing, breaking or resolving emulsions of the water-in-oil type, and particularly petroleum emulsions.

The present invention is a continuation-in-part of my co-pending applications, Serial Nos. 288,743 filed May 19, 1952, 296,084 filed June 27, 1952, and 301,804, filed July 30, 1952.

My invention provides an economical and rapid process for resolving petroleum emulsions of the water-in-oil type, that are commonly referred to as cut oil, roily oil, emulsified oil, etc, and which comprise fine droplets of naturally-occurring waters or brines dispersed in a more or less permanent state throughout the oil which constitutes the continuous phase of the emulsion.

It also provides an economical and rapid process for separating emulsions which have been prepared under controlled conditions from mineral oil, such as Crude-oil and relatively soft waters or weak brines. Controlled emulsification and subsequent demulsification under the conditions just mentioned are of significant value .in removing impurities, particularly inorganic salts, from pipeline oil.

The demulsifyingagents employed in thepresent demulsifying process are the products obtained bythe process of first condensing (a) an oxyalkylation-susceptible, fusible, non-oxygenated organic solvent-soluble, waterinsoluble, low-stage phenolaldehyde resin of the type described hereinafter in Part I; (b) a basic hydroxylated secondary monoamine having not more than 32 carbon atoms in any group attached to'the amino nitrogen atom, and (c) formaldehyde; said condensation reaction being conducted at a temperature sufficiently high to eliminate Water and below the pyrolytic point of the reactants and resultants of reaction; and with theproviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible. The condensation reaction is followed by an oxyalkylation step by means of an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide to form the present demulsifying agents.

In many instances and for various purposes, particularly for the resolution of petroleum emulsions of the water-in-oil type, one may combine a comparatively large proportion of the alkylene oxide, particularly propylene oxide, with a comparatively small proportion of .theresin condensate. In some instances the ratio by weight has been as high as 50 to 1, i. e., the ultimate product of reaction contained approximately 2% of resin condensate and approximately 98% of alkylene oxide.

This invention in a more limited aspect as far as the reactants are concerned which are subjected to oxyalkylation are certain amine-modified thermoplastic phenolaldehyde resins. Such aminemodified resins are described in the aforementioned,copendingapplications and much that is said herein is identical with thetext of, said aforementioned co-pending applications, however, some detail is omitted since the art is; aware of these. resins through my mentioned copending-application, e. g., S; N. 296,084. .Eorupurposeof simplicity the .invention, purely 2,695,888 Patented Nov. 30, 1954 from a standpoint of the resin condensate involved, may be exemplified by an idealized formula as follows:

in which R represents an aliphatic hydrocarbon substituent generally having 4 and not over 18 carbon atoms but most preferably not over 14 carbon atoms, and 21. generally is a small whole number varying from 1 to 4. in the resin structure it is shown as being derived from formaldehyde although obviously other aldehydes are equally satisfactory. The amine residue in the above structure is derived from a basic amine, and usually a strongly basic amine, and may be indicated thus:

RI HN in which R represents any appropriate hydrocarbon radical such as an ,alkyl, alicyclic, arylalkyl radical, etc., with the proviso that at least one of the radicals designated by R has at leastpne hydroxyl radical. The hydrocarbon radical may'hav the carbon atom chain or equivalent interrupted by oxygen atoms. The only limitation is that the radical should not have a negative radical which considerably reduces the 'basicity of the amine, such as an aryl radical or an 'acyl'r'adical. The introduction of two such amino radicals into a comparatively small resin molecule, for instance, one having 3 to 6 phenolic nuclei as specified, alters the resultant product in a number of ways. In the first place, a basic nitrogen atom, of course, adds a hydrophile elfect; in the second place, depending on the size o'f' the radical R, there may be a counterbalancing hydrophobe effect or one inwhich the hydrophobe effect more than counterbalances the hydrophile effect of the nitrogen atom. The presence of one or more hydroxyl radicalsintroduces a significant hydrophile effect. Finally, in such cases where R contains one or more oxygen atoms in the form of an ether linkage another effect is introduced, particularly another hydrophile effect. i

I am not aware that it has been previously suggested to modify by oxyalkylation of the resin condensates 'of the kind described herein and in my copending application S. N. 296,084. The condensation product obtained according to the present invention is heat stable, and, in fact, one of its outstanding qualities is that it can be subjected to oxyalkylation, particularly oxyethylation or oxypropylation, under conventional conditions, i. e., presence of an alkyline catalyst, for example, but in any event at a temperaturefabove C. without becoming an insoluble mass.

Any reference, as in the hereto appended claims, to the procedure employed inthe process is not intended to limit the method or order in which the reactants are added, comming'led or reacted. Theprocedure has been referred to as a condensation processfor obvious reasons. As pointed out elsewhere it is my. preference to dissolve theresin in a suitableYsolvent, addthe amine, and then add the formaldehyde as a 37% solution. However, all three reactants can be added in any order. I am inclined to believe that in the presence of abasic catalyst, such as the amine employed, that the formaldehyde produces methylol groups attached to. the phenolic nuclei which, in turn, react with theamine. It would be immaterial, of course, if the formaldehyde reacted with the amine so as to introduce a methylol group attached to nitrogen which, in turn ,would react with the resin molecule. Also, it would be immaterial if both types of compounds were formed which reacted with each other with the evolution of a mole of formaldehyde available for further reaction. Furthermore, a reaction could take place in which no n in which the characters have their previous significance, and n is the integer or a small whole number, with 4 Reference is again made to U. S. Patent 2,499,368 dated March 7, 1950, to De Groote and Keiser. In said immediately aforementioned patent the following test appears:

The same is true in regard to the oxyalkylated resins herein specified, particularly in the lower stage of oxyalkylation, the so-called sub-surface-active stage. The surface-active properties are readily demonstrated by producing a xylene-water emulsion. A suitable procedure is as follows: The oxyalkylated resin is dissolved in an equal weight of xylene. Such 5050 solution is then mixed with 1-3 volumes of water and shaken to produce an emulsion. The amount of xylene is invariably sufficient to reduce even a tacky resinous product to a solution which is readily dispersible. The emulsions so produced are usually xylene-in-water emulsions (oil-in-water type) particularly when the amount of distilled water used is at least slightly in excess of the volume of xylene solution and also if shaken vigorously. At times, parthe proviso that in each terminal amino radical there ticlllfly 111 the lowest Stage of P Y Y P (2116 y must be at least one hydroxyl group. obtain a water-in-xylene emuls1on (water-m-oil type) Thus, one can show that oxyalkylation can take place which is apt to reverse on more vigorous shaking and not only at the phenolic hydroxyl but also at the amino further dilution with water. group hydroxyl in the following manner: If in doubt as to this property, comparison with a in which for simplicity the formula just shown previously resin obtained from para-tertiary butylphenol and form has been limited to the specific instance where there is aldehyde (ratio 1 part phenol to 1.1 formaldehyde) usonly one hydroxyl in the amino radical. In the above 40 ing an acid catalyst and then followed by oxyalkylation formula RO is the radical of alkylene oxide, such as the using 2 moles of ethylene oxide for each phenolic hyethoxy, propoxy or similar radicals derived from glycide droxyl, is helpful. Such resin prior to oxyalkylation has ethylene oxide, propylene oxide, or the like, and n is a a molecular weight indicating about 4 /2 units per resin number varying from 1 to 60, with the proviso that one molecule. Such resin, when diluted with an equal weight need not oxyalkylate all the available phenolic hydroxyl of xylene, will serve to illustrate the above emulsificaradicals or all the available hydroxyls which are part of tion test. the amino radical. In other words, one need convert In a few instances, the resin may not be sufliciently only two hydroxyl radicals per condensate unit. It is soluble in Xylene alone but may require the addition of immaterial whether they are phenolic hydroxyls or hysome ethylene glycol diethylether as described elsewhere. droxyls which are part of the amino radical. Stated 0 It is understood that such mixture, or any other similar another way, n can be zero as well as a whole number mixture, is considered the equivalent of xylene for the subject to what has been said immediately preceding, all purpose of this test. of which will be considered in greater detail subsequently. In many cases, there is no doubt as to the presence As far as the use of the herein described ultimate or absence of hydrophile or surface-active characterisproducts goes for purpose of resolution of petroleum tics in the products used in accordance with this invenemulsions of the water-in-oil type, I particularly prefer to tion. They dissolve or disperse in water; and such disuse those which as such merely as a result of oxyalkylapersions foam readily. With borderline cases, i. e., those tion alone, or in the form of the free base or hydrate, i. e., which show only incipient hydrophile or surface-active combination with water or particularly in the form of a property (sub-surface-activity) tests for emulsifying low molal organic acid such as the acetate or hydroxy 69 properties or self-dispersibility are useful. The fact that acetate, have sufiiciently hydrophile character to at least a reagent is capable of producing a dispersion in water meet the test set forth in U. S. Patent No. 2,499,368, is proof that it is distinctly hydrophile. In doubtful dated March 7, 1950,- to De Groote et al. In some incases, comparison can be made with the butylphenolstances oxyalkylation is the controlling factor rather than formaldehyde resin analog wherein 2 moles of ethylene the basic nitrogen atoms present regardless of their strucoxide have been introduced for each phenolic nucleus. ture or combination. In said patent such test for emulsi- The presence of xylene or an equivalent water-infication using a water-insoluble solvent, generally xylene, soluble solvent may mask the point at which a solventis described as an index of surface activity. free product on mere dilution in a test tube exhibits In the present instance the various oxyalkylated conself-emulsification. For this reason, if it is desirable to densation products as such or in the form of the free 70 determine the approximate point where self-emulsificabase or in the form of the acetate, may not necessarily tion begins, then it is better to eliminate the xylene or be Xylene-Soluble although y are 111 3 P equivalent from a small portion of the reaction mixture If 511E311 comRollnds are y m the ObVlOllS and test such portion. In some cases, such xylene-free chemical equivalent or equivalent chemical test can be resultant may show initial or incipient hydrophile propmade y p y 115mg some Sultable Solvent, P Y erties, whereas in presence of xylene such properties a water'soluble Solvent Such as ethylelle glycol y would not be noted. In other cases, the first objective fis a 1110181 h a ,mlXtllT t0 dISSOIYC indication of hydrophile properties may be the capacity 9 PP P Pf belllg eXamlned and e m of the material to emulsify an insoluble solvent such as g t glil fi t i g 3 $3 1 ;t lfOllQWfid f y agdltloll 0f xylene. It is to be emphasized that hydrophile properthat {here 11 0 Y e of t reason ties herein referred to are such as those exhibited by v W0 P ases 011 E P Shakmg and inclprent self-emulsification or the presence of emulsifysurface activity makes 1ts presence manifest. It s uning properties and go through the range of homogeneous derstood the referencem tne hereto appended clalms as dispersibility or admixture with water even in presence of to the use of xylene 1n the emulsification test includes added water-insoluble solvent and minor proportions of such obvious variant. common electrolytes as occur in oil field brines.

Elsewhere, it is pointed out that an emulsification test may be used to determine ranges of surface-activity and that such emulsification tests employ a xylene solution. Stated another way, it is really immaterial whether a xylene solution produces a sol or whether it merely produces an emulsion.

For convenience, the subsequent text will be divided into five parts.

Part 1 is concerned with the general structure of the amine-modified resin condensates and also the resin itself, which is used as a raw material;

Part 2 is concerned with the appropriate basic hydroxylated secondary monoamines which may be employed in the preparation of the herein described aminemodified resins;

Part 3 is concerned with the condensation reactions involving the resin, the amine, and formaldehyde to produce the specific products or compounds;

Part 4 is concerned with the oxyalkylation of the products described in Part 3, preceding; and

Part 5 is concerned with the use of the oxyalkylated amine-modified resins obtained as described in Part 4, preceding, for use in the resolution of emulsions of the water-in-oil type.

In the subsequent text, Parts 1, 2 and 3 appear in substantially the same form as in the text of the aforementioned copending applications, Serial Nos. 288,743, filed May 19, 1952, 296,084, filed June 27, 1952, and 301,804, filed July 30, 1952. Furthermore, Part 4 is essentially the same as Part 4 in the last aforementioned co-pending application, i. e., Serial No. 301,804, filed July 30, 1952.

PART 1 It is well known that one can readily purchase on the open market, or prepare, fusible, organic solvent-soluble, water-insoluble resin polymers of a composition approximated in an idealized form by the formula In the above formula n represents a small whole number varying from 1 to 6, 7 or 8, or more, up to probably 10 or 12 units, particularly when the resin is subjected to heating under a vacuum as described in the literature. A limited sub-genus is in the instance of low molecular weight polymers where the total number of phenol nuclei varies from 3 to 6, i. e., n varies from 1 to 4; R repre sents an aliphatic hydrocarbon substituent, generally an alkyl radical having from 4 to 14 carbon atoms, such as a butyl, amyl, hexyl, decyl or dodecyl radical. Where the divalent bridge radical is shown as being derived from formaldehyde it may, of course, be derived from any other reactive aldehyde having 8 carbon atoms or less.

Because a resin is organic solvent-soluble does not mean it is necessarily soluble in any organic solvent. This is particularly true where the resins are derived from trifunctional phenols as previously noted. However, even when obtained from a difunctional phenol, for instance para-phenylphenol, one may obtain a resin which is not soluble in a nonoxygenated solvent, such as benzene, or xylene, but requires an oxygenated solvent such as a low molal alcohol, dioxane, or diethylglycol diethylether. Sometimes a mixture of the two solvents (oxygenated and nonoxygenated) will serve. See Example 9a of U. S. Patent No. 2,499,365, dated March 7, 1950, to De Groote and Keiser.

The resins herein employed as raw materials must be soluble in a nonoxygenated solvent, such as benzene or xylene. This presents no problem insofar that all that is required is to make a solubility test on commercially available resins, or else prepare resins which are xylene or benzene-soluble as described in aforementioned U. S. Patent No. 2,499,365, or in U. S. Patent No. 2,499,368 dated March 7, 1950, to De Groote and Keiser. In said patent there are described oxyalkylation-susceptible,

fusible, nonoxygenated-organic solvent-soluble, water-insoluble, low-stage phenol-aldehyde resins having an, av-' erage molecular weight corresponding to atleast 3. and, not over 6 phenolic nuclei per resin molecule in which R is an aliphatic hydrocarbon radical having at least 4 carbon atoms and not more than 24 carbon atoms and substituted in the 2,4,6 position. The phenol aldehyde resins are difunctional only in regard to methylolforming reactivity, and the resins are derived by reac-' tion between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward the phenol. Also, the resins are formed in the substantial absence of trifunctional phenols. The phenol constituent of the resins is ofthe formula If one selected a resin of the kind just described previously and reacted approximately one mole of the resin with two moles of formaldehyde and two moles of a basic hydroxylated secondary amine as specified, following the same idealized over-simplification previously referred to, the resultant product might be illustrated thus:

The basic hydroxylated amine may be designated thus:

RI HN In conducting reactions of this kind one does not necessarily obtain a hundred per cent yield for obvious reasons. Certain side reactions may take place. For instance, 2 moles of amine may combine with one mole of the aldehyde, or only one mole of the amine may combine with the resin molecule, or even to a very slight extent, if at all, 2 resin units may combine without any'amine in the reaction product, as indicated in the following formulas:

As has been pointed out previously, as far as the resin unit goes one can use a mole of aldehyde other than formaldehyde, such as acetaldehyde, propionaldehyde or butyraldehyde. The resin unit may be exemplified RV 111R" 7 in which R' is the divalent radical obtained from the particular aldehyde employed to form the resin. For reasons which are obvious the condensation product obtained appears to be described best in terms of the method of manufacture.

As previously stated the preparation of resins, the the kind herein employed as reactants, is well known. See previously mentioned U. S. Patent 2,499,368. Resins can be made using an acid catalyst or basic catalyst or a catalyst having neither acid nor basic properties in the ordinary sense or without any catalyst at all. It is preferable that the resins employed be substantially neutral. In other words, if prepared by using a strong acid as a catalyst, such strong acid should be neutralized. Similarly, if a strong base is used as a catalyst it is preferable that the base be neutralized although I have found that sometimes the reaction described proceeded more rapidly in the presence of a small amount of a free base. The amount may be as small as at 200th of a percent and as much as a few lths of a percent. increase in caustic soda and caustic potash may be used. However, the most desirable procedure in practically every case is to have the resin neutral.

In preparing resins one does not get a single polymer, i. e., one having just 3 units, or just 4 units, or just 5 units, or just 6 units, etc. It is usually a mixture; for instance, one approximating 4 phenolic nuclei will have some trimer and pentamer present. Thus, the molecular weight may be such that it corresponds to a fractional value for n as, for example 3.5, 4.5 or 5.2.

In the actual manufacture of the resins I found no reason for using other than those which are lowest in price and most readily available commercially. For purposes of convenience suitable resins are characterized in the following table:

TABLE I $01.f Ex. Position R derived R n resin No. of R frommole cule 1a.-- Phenyl Para Formaldehyde 992.5 2a Tertiary butyl -d0 d0 8 Secondary butyl. Oyclo hexyl 5a.-. Tertiary amyl 959: 5 Ga"- Mixed secondary 805. 5

and tertiary amyl.

1311.. Tertiary butyl.

14a Tertiary amyl 1511.. Nonyl 1, 330. 5 1611-. Tertiary butyl. 1, 071.5 1711-- Tertiary amyL. 1, 148. 5 18a. N onyl 1, 456. 5 19a.-. Tertiary buty 1, 008. 5 20a Tertiary amyl 1, 085.5 2111-. Nonyl 1, 393. 5 22a Tertiary butyL 996. 6 2311.. Tertiary amyL. 1,083. 4 24a Nonyl 1, 430. 6 2511.- Tertiary butyl. 1, 094. 4 26a Tertiary amyl 1, 189. 6 27a Nonyl. 1, 570. 4

Part 2 As has been pointed out previously the amine herein employed as a reactant is a basic hydroxylated secondary monoamme whose composition is indicated thus:

in which R represents a monovalent alkyl, alicyclic, arylalkyl radical which may be heterocyclic in a few instances as in a secondary amine derived from furfurylamine by reaction of ethylene oxide or propylene oxide.

Sometimes moderate A Furthermore, at least one of the radicals designated by R must have at least one hydroxyl radical. A large number of secondary amines are available and may be suitably employed as reactants for the present purpose. Among others, one may employ diethanolamine, methyl ethanolamine, dipropanolamine and ethylpropanolamine. Other suitable secondary amines are obtained, of course, by taking any suitable primary amine, such as an alkylamine, an arylalkylamine, or an alicyclic amine, and treating the amine with one mole of an oxyalkylating agent, such as ethylene oxide, propylene oxide, butylene oxide, glycide, or methylglycide. Suitable primary amines which can be so converted into secondary amines, include butylamine, amylamine, hexylamine, higher molecular weight amines derived from fatty acids, cyclohexylamine, benzylamine, furfurylamine, etc. In other instances secondary amines which have at least one bydroxyl radical can be treated similarly with an oxyalkylating agent, or for that matter, with an alkylating agent such as benzylchloride, esters of chloroacetic acid, alkyl bromides, dimethylsulfate, esters of sulfonic acid, etc., so as to convert the primary amine into a secondary amine. Among others, such amines include 2-amino-1- butanol, Z-amino-Z-methyl-l-propanol, 2-amino-2-methyl-l,3-propanediol, 2-amino-2-ethyl-1,3-propanediol, and trie-(hydroxymethyl)-aminomethane. Another example of such amines is illustrated by 4-amino-4-methyl-2- pentanol.

Similarly, one can prepare suitable secondary amines which have not only a hydroxyl group but also one or more divalent oxygen linkages as part of an ether radical. The preparation of such amines or suitable reactants for preparing them has been described in the literature and particularly in two United States patents, to wit, U. S. Patents Nos. 2,325,514 dated July 27, 1943, to Hester, and 2,355,337 dated August 8, 1944, to Spence. The latter patent describes typical haloalkyl ethers such as CHsO 0211 01 CHr-OHa CH2 CH-CHzO 021140 02114131 0 CzHaO C2H O 0235 0 021340 0211 01 Such haloalkyl ethers can be reacted with ammonia or with a primary amine, such as ethanolamine, propanolamine, monoglycerylamine, etc., to produce a secondary amine in which there is not only present a hydroxyl radical but a repetitious ether linkage. Compounds can be readily obtained which are exemplified by the following formulas:

(C2H5O CIHAO C2H4) /NH HO C2114 (CBHl'IOClHAOOlHAOCBHI) HO C2114 (C4H90 CH2CH(CH3) 0 (011a) CHCHfl) NH HO CQHA (CH3O CH1CH2O CHzCHaO CHICHZ) HO 02H;

(OHIO CHzCHzCHaCHzCHzCHz) HO C2114 or comparable compounds having two hydroxylated groups of diflerent lengths as is (HOCHZCHtOCHzCHaOCHzCHz) /NH HOCsHt Other examples of suitable amines include benzylethanolamine and methylethanolamine; also amines obtained by treating cyclohexylznethylamine with one mole of an oxyalkylating agent as previously described; betaethylhexyl-butanolamine, diglycerylamine, etc. Another type of amine which is of particular interest because it includes a very definite hydrophile group includes sugar amines such as glucamine, galactamine and fructamine, such as N-hydroxyethylglucamine, N-methylglucamine, N -hydroxyethylgalactamine, and N-hydroxyethylfructamine.

Other suitable amines may be illustrated by See, also, corresponding hydroxylated amines which can be obtained from rosin or similar raw materials and described in U. S. Patent No. 2,510,063, dated June 6, 1950, to Bried. Still other examples are illustrated by treatment of certain primary amines, such as the following, with a mole of an oxyalkylating agent as described; phenoxyethylamine, phenoxypropylamine, phenoxyalphamethylethylamine, and phenoxypropylamine.

Other procedures for production of suitable compounds having a hydroxyl group and a single basic amino nitrogen atom can be obtained from any suitable alcohol or the like by reaction with a reagent which contains an epoxide group and a secondary amine group. Such reactants are described, for example, in U. S. Patents Nos.

' 1,977,251 and 1,977,253, both dated October 16, 1934,

to Stallmann. Among the reactants described in said latter patent are the following:

PART 3 The products obtained by the herein described processes represent cogeneric mixtures which are the result of a condensation reaction or reactions. Since the resin molecule cannot be defined satisfactorily by formula, although it may be so illustrated in an idealized simplification, it is difficult to actually depict the final product of tlge cogeneric mixture except in terms of the process itsel Previous reference has been made to the fact that the procedure herein employed is comparable, in a general way, to that which corresponds to somewhat similar derivatives made either from phenols as differentiated from a resin, or in the manufacture of a phenol-amine-aldehyde resin; or else from a particularly selected resin and an amine and formaldehyde in the manner described in Bruson Patent No. 2,031,557 in order to obtain a heatreactive resin. Since the condensation products obtained are not heat-convertible and since manufacture is not restricted to a single phase system, and since temperatures up to 150 C. or thereabouts may be employed, it is obvious that the procedure becomes comparatively simple. This procedure is noted in my copending application S. N. 296,084, and further description of certain details is unnecessary.

Needless to say, as far as the ratio of reactants goes I have invariably employed approximately one mole of the resin based on the molecular weight of the resin molecule, 2 moles of the secondary amine and 2 moles of formaldehyde. In some instances I have added a trace of caustic as an added catalyst but have found no particular advantage in this. in other cases I have used a slight excess of formaldehyde and, again, have not found any particular advantage in this. In other cases I have used a slight excess of amine and, again, have not found any particular advantage in so doing. Whenever feasible 1 have checked the completeness of reaction in the usual ways, including the amount of water of reaction, molecular weight, and particularly in some instances have checked whether or not the end-product showed surface-activity, particularly in a dilute acetic acid solution. The nitrogen content after removal of unreacted amine, if any is present, is another index.

In light of what has been said previously, little more need be said as to the actual procedure employed for the preparation of the herein described condensation products. The following example will serve by way of illustration:

Example 1b The phenol-aldehyde resin is the one that has been identified previously as Example 2a. It was obtained from a paratertiary butyl phenol and formaldehyde. The resin was prepared using an acid catalyst which was completely neutralized at the end of the reaction. The molecular weight of the resin was 882.5. This corresponded to an average of about 3 /2 phenolic nuclei as the value for n which excludes the two external nuclei, 1'. e., the resin was largely a mixture having 3 nuclei and 4 nuclei excluding the 2 external nuclei, or 5 and 6 overall nuclei. The resin so obtained in a neutral state had a light amber color.

882 grams of the resin identified as 2:: preceding were powdered and mixed with 700 grams of xylene. The mixture was refluxed until solution was complete. it was then adjusted to approximately 30 to 35 C. and 210 grams of diethanolamine added. The mixture was stirred vigorously and formaldehyde added slowly. The formaldehyde used was a 37% solution and 160 grams were employed which were added in about 3 hours. The mixture was stirred vigorously and kept within a temperature range of 30 to 45 C. for about 21 hours. At the end of this period of time it was refluxed, using a phase-separating trap and a small amount of aqueous distillate withdrawn from time to time and the presence of unreacted formaldehyde noted. Any unreacted formaldehyde seemed to disappear within approximately 3 hours after the refluxing was started. As soon as the odor of formaldehyde was no longer detectible the phaseseparating trap was set so as to eliminate all water of solution and reaction. After the water was eliminated part of the xylene was removed until the temperature reached about 150 C. The mass was kept at this higher temperature for about 3% hours and reaction stopped. During this time any additional water, which was probably water of reaction which had formed, was eliminated by means of the trap. The residual xylene was permitted to stay in the cogeneric mixture. A small amount of the sample was heated on a water bath to remove the excess xylene and the residual material was dark red in color and had the consistency of a sticky fluid or a tacky resin. The overall reaction time was a little over 30 hours. In other instances it has varied from approximately 24 to 36 hours. The time can be reduced by cutting the low temperature period to about 3 to 6 hours.

Note that in Table II following there are a large number of added examples illustrating the same procedure. in each case the initial mixture was stirred and held at a fairly low temperature (30 to 40 C.) for a period of several hours. Then refluxing was employed until the odor of formaldehyde disappeared. After the odor of formaldehyde disappeared the phase-separating trap was employed to separate out all the water, both the solution and condensation. After all the water had been separated enough xylene was taken out to have the final product reflux for several hours somewhere in the range of to C., or thereabouts. Usually the mixture yielded a clear solution by the time the bulk of the water, or all of the water, had been removed.

Note that as pointed out previously, this procedure is illustrated by 24 examples in Table II.

TABLE II Strength of R ti R Max. dis Ex. Resin Amt. formalde- Solvent used we on egcmon till No. used grs. Amine used and amount hyde $0111. and am a g ternrt,

and amt. C.

882 Diethanolarnine, 210 g 37%, 162 g... Xylene, 700 g-.. 22-26 3 147 480 Diethanolamlne, 105 g 37%, 81 g Xylene, 450 g 21-23 28 150 633 o do Xylene, 600 g. 20-22 36 145 441 Dipropanolamlne, 133 g 30%, 100 g Xylene, 400 g. 20-23 34 146 480 l l Xylene, 450 g. 21-23 24 141 633 do l o Xylene, 600 g 21-28 24 145 882 Ethylethanolamine, 178 g 37%, 162 Xylene, 700 g 20-26 24 152 480 Ethylethanolamine, 89 g .l 37%, 81 g Xylene, 450 g 24-30 28 151 633 0 l l l d0 Xylene, 600 g... 22-25 27 147 473 Cyclohexylethanolamine, 143 30%, 1')" Xylene, 450 g. 21-31 31 146 511 dO 37%, 81 (l0 2?-23 36 148 665 do do Xylene, 550 g 20-24 27 152 441 C HOCEH OC2H;

NH, 176 g "do Xylene, 400 g 21-25 24 150 140. 5a 480 C2H5OO2H4OC$H4 N H, 176 g do Xylene, 450 g... -26 26 146 HOC2H4 150..." 9a 595 C2H5OC2H4OC2H NH, 176 g do Xylene, 550 g.-- 21-27 30 147 HOC2H4 16b. 2a 441 HOCIH4OC2H4001H4 N, 192 g. do Xylene, 400 g. 20-22 30 148 HOC2H 17b 5G 480 HOCaHgOCzHrOCzH;

N, 192 g -do d0 20-25 28 150 HOCIH 18b. 14a 591 HOO2H4OO2H4OCzH4 N, 192 g.-- do Xylene, 500 g.-. 21-24 32 149 190. 22a 498 HOCQHiO Cali-LO CE;

N, 192 g. do Xylene, 450 g.-- 22-25 32 153 20b. 23a 542 CH3(OC2H4)3 N, 206 g 30%, 100 g... Xylene, 500 g-.. 21-23 36 151 211)..... a 547 CH|(OC2H4)3 N, 206 g do. do 25-30 34 148 HOOQHA 22b 2a 441 CHs(OC2H4)a N, 206 g ..dr Xylene, 400 g... 22-23 31 146 23!). 595 Deeylethanolamine, 201 g 37%, 81 g Xylene, 500 g. 22-27 24 145 24b 2 391 Decylethanolamlne, 100 g g Xylene, 300 g. 21-25 26 47 PART 4 and a working pressure of 300 pounds gauge pressure.

In preparing oxyalkylated derivatives of products of the kind which appear as examples in Part 3, I have found it particularly advantageous to use laboratory equipment which permits continuous oxypropylation and oxyethylation. More specific reference will be made to treatment with glycide subsequently in the text. The oxyethylation step is, of course, the same as the oxypropylation step insofar that two low boiling liquids are handled in each instance. What immediately follows refers to oxyethylation and it is understood that oxypropylation can be handled conveniently in exactly the same manner.

The oxyethylation procedure employed in the preparation of derivatives of the preceding intermediates has been uniformly the same, particularly in light of the fact that a continuous operating procedure was employed. In this particular procedure the autoclave was a conventional jacketed autoclave, made of stainless steel and having a capacity of approximately 25 gallons,

The autoclave was equipped with the conventional devices and openings, such as the variable speed stirrer operating at speeds from 50 R. P. M. to 500 R. P. M., thermometer Well and thermocouple for recorder controller; emptying outlet, pressure gauge, manual and rupture disc vent lines; charge hole for initial reactants; at least one connection for conducting the incoming alkylene oxide, such as ethylene oxide, to the bottom of the autoclave; along with suitable devices for both cooling and heating the autoclave through the jacket. Also, I prefer coils in addition thereto, with the coils so arranged that they are suitable for heating with steam or cooling with water, and the jacket further equipped with electrical heating devices, such as are employed for hot oil or Dowtherm systems. Dowtherm, more specifically Dowtherm A, is a colorless non-corrosive liquid consisting of an eutectic mixture of diphenyl and diphenyl oxide. Such autoclaves are, of course, in essence, small scale replicas of the usual conventional autoclave used in commercial oxyalkylati s p edure.

Continuous operation, or substantially continuous operation, is achieved by the use of a separate container to hold the alkylene oxide being employed, particularly ethylene oxide. The container consists essentially of a laboratory bomb having a capacity of about to 15 gallons or somewhat in excess thereof. This bomb was equipped, also, with an inlet for charging, and an outlet tube going to the bottom of the container so as to permit discharging of alkylene oxide in the liquid phase to the autoclave. Other conventional equipment consists, of course, of the rupture disc, pressure gauge, sight feed glass, thermometer, connection for nitrogen for pressuring bomb, etc. The bomb was placed on a scale during use and the connections between the bomb and the autoclave were flexible stainless hose or tubing so that continuous weighings could be made without breaking or making any connections. This also applied to the nitrogen line, which was used to pressure the bomb reservoir. To the extent that it was required, any other .usual conventional procedure or addition which provided greater safety was used, of course, such as safety glass, protective screens, etc.

With this particular arrangement practically all oxyethylations became uniform in that the reaction temperature could be held within a few degrees of any selected point in this particular range. In the early stages where the concentration of catalyst is high the temperature was generally set for around 130 C. or thereabouts. Subsequently the temperature may be somewhat higher for instance, 135 C. to 140 C. Under other conditions, definitely higher temperatures may be employed, for instance 170 C. to 175 C. It will be noted by examination of subsequent examples that this temperature range was satisfactory. In any case, where the reaction goes more slowly a higher temperature may be used, for instance, 140 C. to 145 C., and if need be 150 C. to 160 C. Incidentally, oxypropylation takes place more slowly than oxyethylation as a rule and for this reason I have used a temperature of approximately 130 C. to 140 C., as being particularly desirable for initial oxypropylation, and have stayed within the range of 130 C. to 135 C. almost invariably during oxypropylation. The lesser reactivity of propylene oxide compared with ethylene oxide can be oifset by use of more catalyst, more vigorous agitation and perhaps a longer time period. The ethylene oxide was forced in by means of nitrogen pressure as rapidly as it was absorbed as indicated by the pressure gauge on the autoclave. In case the reaction slowed up the temperature was raised so as to speed up the reaction somewhat by use of extreme heat. It need be, cooling water was employed to control the temperature.

As previously pointed out in the case of oxypropylation as differentiated from oxyethylation, there was a tendency for the reaction to slow up as the temperature dropped much below the selected point of reaction, for instance, 135 C. In this instance, the technique employed was the same as before, that is, either cooling water was cut down or steam vas employed, or the addition of propylene oxide speeded up, or electric heat used in addition to the steam in order that the reaction proceeded at, or near, the selected temperatures to be maintained.

inversely, if the reaction proceeded too fast regardless of the particular alkylene oxide, the amount of reactant being added, such as ethylene oxide, was cut down or electrical heat was cut oif, or steam was reduced, or if need be, cooling water was run through both the jacket and the cooling coil. All these operations, of course, are depending on the required number of conventional gauges, check valves, etc., and the entire equipment, as has been pointed out, is conventional and, as far as I am aware can be furnished by at least two firms who specialize in the manufacture of this kind of equipment.

Attention is directed to the fact that the use of glycide requires extreme caution. This is particularlv true on any scale other than small laboratory or semipilot plant operations. Purely from the standpoint of safety in the handling of glycide, attention is directed to the following: (a) If prepared from glycerol monochlorohydrin, this product should be comparatively pure; (b) the glycide itself should be as pure as possible as the effect of impurities is diflicult to evaluate: (cl the glycide should be introduced carefully and precaution should be taken that it reacts as promptly as introduce d, i. .e., that no excess of glycide is allowed to accumulate; (d) all necessary precautions should be taken that glycide cannot polymerize per se; (a) due to the high boiling point of giycide one can readily employ a typical separatable glass resin pot as described in U. S. Patent No. 2,499,370 dated March 7, 1950, and offered for sale by numerous laboratory supply houses. If such arrangement is used to prepare 'laboratory scale duplications, then care should be taken that the heating mantle can be removed rapidly so as to allow for cooling; or better still, through an added opening at the top, the glass resin pot or comparable vessel should be equipped with a stainless steel cooling coil so that the pot can be cooled more rapidly than mere removal of mantle. If a stainless steel coil is introduced it means that conventional stirrer of the paddle type is changed into the centrifugal type which causes the fluids or reactants to mix due to swirling action in the center of the pot. Still better, is the use of a laboratory autoclave of the kind previously described in this part of the text, but in any event, when the initial amount of glycide is added to a suitable reactant, such as the herein described amine-modified phenol-aldehyde resin, the speed of reaction should be controlled by the usual factors, such as (a) the addition of glycide; (b) the elimination of external heat, and (0) use of cooling coil so there is no undue rise in temperature. All the foregoing is merely conventional but is included due to the hazard in handling glycide.

Although ethylene oxide and propylene oxide may represent less of a hazard than glycide, yet these reactants should be handled with extreme care. One suitable procedure involves the use of propylene oxide or butylene oxide as a solvent as well as a reactant in the earlier stages along with ethylene oxide, for instance, by dissolving the appropriate resin condensate in propylene oxide even though oxyalkylation is taking place to a greater or lesser degree. After a solution has been obtained which represents the selected resin condensate dissolved in propylene oxide or butylene oxide, or a mixture which includes the oxyalkylated product, ethylene oxide is added to react with the liquid mass until hydrophile properties are obtained, if not previously present to the desired degree. Indeed hydrophile character can be reduced or balanced by use of some other oxide such as propylene oxide or butylene oxide. Since ethylene oxide is more reactive than propylene oxide or butylene oxide, the final product may contain some unreated propylene oxide or butylene, oxide which can be eliminated by volatilization or distillation in any suitable manner. See article entitled Ethylene oxide hazards and methods of handling, Industrial and Engineering Chemistry, volume 42, N0. 6, June 1950, pp. l1258. Other procedures can be employed as, for example, that described in U. S. Patent No. 2,586,767, dated February 19, 1952, to Wilson.

Example 1::

The oxyalkylation-susceptible compound employed is the one previously described and designated as Example lb. Condensate 1b was in turn obtained from diethanolamine and the resin previously identified as Example 2a. Reference to Table I shows that this particular resin is obtained from paratertiarybutylphenol and formaldehyde. 11.16 pounds of this resin condensate were dissolved in 7 pounds of solvent (xylene) along with one pound of finely powdered caustic soda as a catalyst. Adjustment was made in the autoclave to operate at a temperature of approximately 125 C. to l35 C., and at a pressure of about 15 to 20 pounds.

The time regulator was set so as to inject the ethylene oxide in approximately two hours and then continue stirring for a half-hour or longer. The reaction went readily and, as a matter of fact, the oxide was taken up almost immediately. Indeed the reaction was complete in less than an hour. More specifically it was complete in 45 minutes. The speed of reaction, particularly at the low pressure, undoubtedly was due in a large measure to excellent agitation and also to the comparatively high concentration of catalyst. The amount of ethylene oxide introduced was equal in weight to the initial condensation product, to wit, 11.16 pounds. This represented a molal ratio of 25 moles of ethylene oxide per mole of condensate.

The theoretical molecular weight at the end of the reaction period was 2232. A comparatively small sample, less than 50 grams, was withdrawn merely for examination as far as solubility or emulsifying power was concerned and also for the purpose of maklng some tests on various oil field emulsions. The amount withdrawn was so small that no cognizance of this fact is included in the data, or subsequent data, or in the data presented in tabular form in subsequent Tables 3 and 4.

The size of the autoclave employed was 25 gallons. In innumerable comparable oxyalkylations I have wlthdrawn a substantial portion at the end of each step and continued oxyalkylation on a partial residual sample. This was not the case in this particular series. Certain examples were duplicated as herein after noted and subjected to oxyalkylation with a different oxide.

Example 20 This example simply illustrates the further oxyalkylation of Example 10, preceding. As previously stated, the oxyalkylation-susceptible compound, to wit, Example lb, present at the beginning of the stage was obviously the same as at the end of the prior stage (Example to wit, 11.16 pounds. The amount of oxide present in the initial step was 11.16 pounds, the amount of catalyst remained the same, to wit, one pound, and the amount of solvent remained the same. The amount of oxide added was another 11.16 pounds, all addition of oxide in these various stages being based on the addition of this particular amount. Thus, at the end of the oxyethylation step the amount of oxide added was a total of 22.32 pounds and the molal ratio of ethylene oxide to resin condensate was 50.8 to 1. The

theoretical molecular weight was 3348.

The maximum temperature during the operation was 130 C. to 135 C. The maximum pressure was in the range of to pounds. The time period was one hour.

Example The oxyalkylation proceeded in the same manner described in Examples 10 and 2c. There was no added solvent and no added catalyst. The oxide added was 11.16 pounds and the total oxide at the end of the oxyethylation step was 33.48 pounds. The molal ratio of oxide to condensate was 76.2 to 1. Conditions as far as temperature and pressure and time were concerned were all the same as in Examples 1c and 2c. The time period was somewhat longer than in previous examples, to wit, 2 hours.

Example 4c The oxyethylation continued with the introduction of another 11.16 pounds of ethylene oxide. No more solvent was introduced but .3 pound caustic soda was added. The theoretical molecular weight at the end of the agitation period was 6696, and the molal ratio of oxide to resin condensate was 127 to 1. The time period, however, dropped to 1% hours. Operating temperature and pressure remained the same as in the previous example.

Example 6c The same procedure was followed as in the previous examples except that an added pound of powdered caustic soda was introduced to speed up the reaction. The amount of oxide added was another 11.16 pounds, bringing the total oxide introduced to 66.96 pounds. The temperature and pressure during this period were the same as before. There was no added catalyst and also no added solvent. The time period was 2% hours.

Example 7c The same procedure was followed as in the previous six examples without the addition of more caustic or more solvent. The total amount of oxide introduced at the end of the period was 78.12 pounds. The theoretical molecular weight at the end of the oxyalkylation period was 8928. The time required for the oxyethylation was a bit longer than in the previous step, to wit, 3 hours.

Example 80 This was the final oxyethylation in this particular series. There was no added solvent and no added catalyst. The total amount of oxide added at the end of this step was 89.28 pounds. The theoretical molecular weight was 10,044. The molar ratio of oxide to resin condensate was 203.2 to one. Conditions as far .as temperature and pressure were concerned were the same as in the previous examples and the time required for oxyethylation was 4 hours.

The same procedure as described in the previous examples are employed in connection with a number of the other condensates described previously. All'these data have been presented in tabular form in a series of four tables, Tables III and IV, V and VI.

In substantially every case a 25-gallon autoclave was employed, although in some instances the initial oxyethylation was started in a lS-gallon autoclave and then transferred to a 25-gallon autoclave. This is immaterial but happened to be a matter of convenience only. The solvent used in all cases was xylene. The catalyst used was finely powdered caustic soda.

Referring now to Tables III and IV, it will be noted that compounds 1c through 40c were obtained by the use of ethylene oxide, whereas 410 through 800 were obtained by the use of propylene oxide alone.

Thus, in reference to Table III it is to be noted as follows:

The example number of each compound is indicated in the first column.

The identity of the oxyalkylation-susceptible compound, to wit, the resin condensate, is indicated in the second column.

The amount of condensate is shown in the third column.

Assuming that ethylene oxide alone is employed, as happens to be the case in Example 1c through 400, the amount of oxide present in the oxyalkylation derivatives is shown in column 4, although in the initial step since no oxide is present there is a blank.

When ethylene oxide is used exclusively the 5th column is blank.

The 6th column shows the amount of powdered caustic soda used as a catalyst, and the 7th column shows the amount of solvent employed.

The 8th column can be ignored where a single oxide was employed.

The 9th column shows the theoretical molecular weight at the end of the oxyalkylation period.

The 10th column states the amount of condensate present in the reaction mass at the end of the period.

As pointed out previously, in this particular series the amount of reaction mass withdrawn for examination was so small that it was ignored and for this reason the resin condensate in column 10 coincides with the figure in column 3.

Column 11 shows the amount of ethylene oxide employed in the reaction mass at the end of the particular period.

Column 12 can be ignored insofar that no propylene oxide was employed.

Column 13 shows the catalyst at the end of the reaction period.

Column 14 shows the amount of solvent at the end of the reaction period.

Column 15 shows the molal ratio of ethylene oxide to condensate.

Column 16 can be ignored for the reason that no propylene oxide was employed.

Referring now to Table VI. It is to be noted that the first column refers to Examples 10, 20, 30, etc.

The second column gives the maximum temperature employed during the oxyalkylation step and the third column gives the maximum pressure.

The fourth column gives the time period employed.

The last three columns show solubility tests by shaking a small amount of the compound, including the solvent present, with several volumes of water, xylene and kerosene. It sometimes happens hat although xylene in com"- paratively small amounts will dissolve in the concentrated 18" present from the first oxyalkylation step plus added catalyst, if any. The same is true in regard to the solvent. Reference to' the solvent refers to the total solvent present, i. e., that from the first oxya'lkylation step plus added material, when the concentrated material in turn isdiluted solvent; ifany. wlth Xylene separation takes place. I In this series,- it will be noted that the theoretical mole- Referring to Table IV, Examples 410 through 800 are cular weights are given prior to the oxyalkylation step and the counterparts of Examples through 40c, except that after the oxyalkylation step, although the value at the end the oxide employed is propylene oxide instead of ethylene of one step is the value at the beginning of the next step, oxide. Therefore, as explained previously, four columns 10 except obviously at the very start the value depends on are blank, to wit, columns 4", 8, 11 and 15. the theoretical molecular weight at the end of the initial Reference is now made to Table V. It is to be noted oxyalltyl'ation step; i. e., oxyethyla'tion for 1d through these compounds are designated by d numbers, 131, 2d, 16d, and oxypropylation for 17d through 32d. 3d, etc., through and lncluding 32d. They are derived, in It will he noted also that underthe molal ratio the turn, from compounds in the c series, for example, 350, values of both oxides to the resin condensate are included. 390, 53c and 620. These compounds involve the use of The data given in regard to the operating conditions is both ethylene oxide and propylene oxide. Since co'm= substantially the same as before and appears in Table VI. pounds 10 through 400 were obtained by the use of ethyl- The products resulting from these procedures may conene oxide, it is obvious that those obtained from 35c and tain modest amounts, or have small amounts, of the 390, involve the use of ethylene oxide first, and propylene 20 solvents as indicated by the figures 1n the tables. If oxide afterward. Inversely, those compounds obtained desired the solvent may be removed by distillation, and from 530 and 620 obviously came from a prior series in particularly vacuum distillation. Such distillation also which propylene oxide was used first. may remove traces or small amounts of uncombined' In the preparation of this series indicated by the small I oxide, if present and volatile under the conditions em letter d, as 1d, 2d, 321, etc., the in1tial 0 series such as ployed, 3 0 and e pl p the y yl Obviously, in the use of ethylene oxide and propylene Stopped the PQ dfislgnated lnsfiead 0f P 8 oxide in combination one need not first use one oxide and earned further as may have been the case 1n the orlginal they the other, but one can mix the two Oxides thus PXyalkylatlon .Jxyalkylatlon Pmfeeded by obtain what may be termed an indifferent oxyalkylation, 9 thfi seixmd oxlde as mfhcilted by h previous g i. e., no attempt to selectively add' one and then the other, tron, to wit, propylene oxide in 1a through 16d, and ethyl- 17d th h 32d l or any other variant. ens OX1 roug i V Needless to say, one could start with ethylene oxide In examining the table begmnmg with 1d, 1twill be and then use to lane oxide and the 0 b ck t 6th I noted that the initial product, i. e., 350, consisted of the g 1 n a reaction product involving 11.16 pounds of the resin con- 35 ene P PrOPY en densate, 16.74 pounds of ethylene oxide, 1.0 pound of use ethylene Oxlde: fll g b PP f i caustic Soda, and 7 pounds f the solvent or, one could use a combina'non in which butylene oxlde It is to be noted that reference to the catalyst in Table used along Wlth; l r 9 of the two J Ineli- V refers to the total amount of catalyst, i. e., the catalyst tioned, or a combination of both of them.

TABLE III Composition before Composition at end Molal ratio to o-s* Ethl. Propl. Oatas01- Theo. Theo. 03* E101. Prop]. Catas01- resln condensate H1158? cmpd oxide, oxide, lyst, vent, mol, nlol. cmpd oxide, ox de, lyst, vent, 7

lbs. lbs. lbs. lbs. lbs. wt. wt. lbs. lbs. lbs. lbs. lbs. EthyL PmDL oxide oxide *Oxyallrylation-susceptible.

TABLE IV Composition before Composition at end.

Molal ratio to o-s* Ethl. Propl. Cata- Sol- Theo. Theo. o-s* Ethl. Propl. Cata- Solcmdensate cmpd., oxide, oxide, lyst, vent, moi. moi. cmpd., oxide, oxide, lyst, vent,

lbs. lbs. lbs. lbs. lbs. wt. Wt. lbs. lbs. lbs. lbs. lbs. Ethyl Prom oxide oxide *Oxyalkylation-susceptible.

TABLE V Composition before Composition at end Molal ratio to 3% o-s* Ethl. Propl. Cato- Sol- Theo. Theo. o-s* Ethl. Pro 1. Cata- 801- mm wndensate cmpd., oxide, oxide, lyst, vent, mol. mol. ompd., oxide, oxi e, lyst, vent, lbs. lbs. lbs. lbs. lbs. wt. wt. lbs. lbs. lbs. lbs. lbs. Ethyl PropL oxide oxide 'Oxyalkylation-susceptibie.

21 22 TKBLE TABLE. VI-Continued Solubility? Solubility M M3 Max. 5. ten? 1352;. t r p temg preS. 3:? 1,. a 4 p.511. W Xylene, Kerosene 5 C S i Water Xylene. Kerosene 1c 125-135 -20 6) 5-10 as 5-10 5-10 llnsoluble. 15 Emulsifia'ble. 'Solub1e; 2% Dispersible, a 4; The colors of'the products usually'vary from a reddish. amber tint to a definitely red; andamber. The: reason is primarily that no effort is made to obtain colorless resins. 1% initially and the resins themselves may be yellow, amber, or even dark amber. Condensation of a nitrogenous 3 product invariably yields a darker product than the 32 original resin and usually' has a reddish color. The solvent employed, if xylene, adds. nothing to the color but 1: one may use a darker colored aromatic petroleum sol- 2% vent. Oxyalkylation' generally tends to yield lighter. 2 colored. products and the morev oxide. employed. the. 1 lighter the color of the. product. Products can be. pre- 4 I pared in: which the final. color is a. lighter amber with a. reddish. tint. Such. products: can be. decolori'zed' by the. use. of clays, bleachingcharsctc. As. far as use in demulsification. is concerned, or some other industrial. uses, there. is no justifi'cation for the cost of bleaching tlie. product.

' be" diluted: as desired with any suitable solvent.

Generally speaking, the amount of alkaline. catalyst present is comparatively small and it need not be. removed. Since the products per se are alkaline due to the presence of a basic nitrogenv atom, the removal of'the alkaline catalyst is somewhat more difficult than. ordinarily is the case. for the reason. that if'one. adds hydrochloric acid', for example, to neutralize the alkalinity one may partially neutralize the basic nitrogen radical also. The preferred procedure is, to ignore the presence oi the alkali. unlessitis objectionable or. else add astoichiometric amount of concentrated. hydrochloric acid equal. to thecaustic sodapresent.

PART 5 In practicing the present process, the treating. or demulsifying, agent is used in the conventional way, well known to the art, described, for example, in Patent 21626329; dated January 27,v 1953,, Part 3.; and. refer.- ence is made thereto for adescri'ption. of. conventional procedures of demulsifying, including batch, continuous, and down-the-hole demulsification, the. process essentially involving introducing a small amount of demulsifi'er into a large amount of emulsion. with adequate admixture with or without the application of heat, and allowing the mixture to stratify.

In many instances the oxyalkylated products herein specified as demulsifiers can be conveniently used without dilution. However, as previously noted, they nlgay or intance, by mixing parts by'weight of an:oxyalkylated derivative, for example, theproduct of Example 3c with 15=parts by weight of xylene and 1.0-parts by weight of isopropyl alcohol, an excellent demulsifier is obtained. Selection of the solvent will vary, depending. upon the solubility characteristics of the-oxyalkylatcd product, and of course will be dictated in part. by economic considerations; i; e., cost.

As noted above, the products herein described may be used not only in diluted form, but also may be used admixed with some other chemical demulsifier. A mixture.which;illustrates such combination is the following:

Oxyalkylated derivative, for example, the product of Example 3c, 20%;

A cyclohexylamine salt of a polypropylated naphthalene monosulfonic acid, 24%;

An ammonium salt of; a polypropylateclnaphthalene monosulfonic acid, 24%;

A sodium salt of oil-soluble. mahogany petroleum sultonic. acid, 12%;:

A high-boiling aromatic petroleum solvent, 15%;

Isopropyl alcohol,

The above proportions are all weight percents.

Having thus described my invention, what I claim as new and desire to obtain by Letters Patent, is:

l. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including the products obtained in the process of first condensing (a) an oxyalkylation-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-aldehyderesin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic hydroxylated secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom, and (0) formaldehyde; said condensation reaction being conducted at a temperature sufliciently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; and with the proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible; followed by an oxyalkylation step by means of an alphabeta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide.

2. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including the products obtained in the process of first condensing (a) an oxyalkylation-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular Weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic hydroxylated secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom, and (0) formaldehyde; said condensation reaction being conducted at a temperature sufficiently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge connecting the amino nitrogen atom with a resin molecule; with the further proviso that the ratioof reactants be approximately 1, 2 and 2 respectively; with the final proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible; followed by an oxyalkylation step by means of an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class and 24 consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide.

3. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including the products obtainedjn the process of first condensing (a) an oxyalkylation-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3v and not over 6 phenolic nuclei resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8' carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which? R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic hydroxylated secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom, and (c) formaldehyde; said condensation reaction being conducted at a temperature sufliciently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction, with the proviso that the condensation reaction 'be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge connectin the amino nitrogen atom with a resin molecule; with t e added proviso that the ratio of reactants be approximately, 1, 2 and 2 respectively; with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation prolduct resulting fr m the process be beatstable and oxyalkylation-susceptib e; followed by an oxyalkylation step by means of an alpha-betazalkylene oxide having not more-I than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide.

4. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including the products obtained in the process of first condensing (a) an oxyethylation-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-formaldehyde resin having an average molecular weight corresponding to'at, least 3 and notover 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and formaldehyde; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of lthe formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic hydroxylated secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom, and (c) formaldehyde; said condensation reaction being conducted at a temperature sufficiently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction, with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge connecting the amino nitrogen atom with a resin molecule; with the added proviso that the ratio of reactants be approximately 1, 2 and 2, respectively; with the further proviso that said procedure involve the use of a.solvent; and withthe final proviso thatthe resinous '25 .condensation product resulting from the process be heat stable and oxyalkylation-susceptible; followed by an oxy "alkylation step by means of :n alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide.

'5. Aprocess for breaking petroleum emulsions of the water-in-oil type characterized by'subjecting the emulsion to the action of a demulsifier including the products obtained in the process of first condensing (a) an oxy- 'et'hylation-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-forma'ldehyde resin having an average molecular weight corresponding to at least 3 and not over '6 phenolic nuclei 'per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol "and formaldehyde; said resin being formed in the substantial absence of trifunct-ional phenols, said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at :least 4 and not more than 14 carbon atoms and vsub-- stituted in the 2,4,6 position; (b) a basic hydroxylated secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom, and (c) formaldehyde; said condensation reaction being conducted at a temperature sufiiciently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction, with the proviso that the condensation reaction be conducted so .as to produce -a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge connecting the .amino nitrogen atom with a resin molecule; with the added proviso that the ratio of reactants be approximately 1, 2 and 2, respectively; with "the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from "the process be heatstable and oxyalkylation-susceptible; followed by an oxy alkylation step by means of an alpha-beta alkylene oxide .having not more than 4 carbon atoms and selected from the 'class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide.

6. A process for breaking petroleum emulsions of the waterin-oil type characterized by subjecting the emulsion to the action of a demulsifier including the products obtained in the process of first condensing (a) an oxyethylation-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-formaldehyde resin having an average molecular weight corresponding to at least 3 and not over 5 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and formaldehyde; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge connecting the amino nitrogen atom with a resin molecule; with the added proviso that the ratio of reactants be approximately 1, 2 and 2, respectively; with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be heatstable and oxyalkylation-susceptible; followed by an oxyalkylation step by means of an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide.

7. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including the products obtained in the process of first condensing (a) an oxyethylation-susceptible, fusible, non-oxygenated organic solventsoluble, Water-insoluble, low-stage phenol-formaldehyde resin having an average molecular weight corresponding to at least 3 and not over 5 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and formaldehyde; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 14 carbon atoms and substituted in the 2,4,6 position; (b) a basic hydroxylated secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom, and (0) formaldehyde; said condensation reaction being conducted at a temperature above the boiling point of water and below C., with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge connecting the amino nitrogen atom with a resin molecule; with the added proviso that the ratio of reactants be approximately 1, 2 and 2, respectively; with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible; followed by an oxalkylation step by means of an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide.

8. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including the products obtained in the process of first condensing (a) an oxyethylation-susceptible, fusible, non-oxygenated organic solventsoluble, water-insoluble, low-stage phenol-formaldehyde resin having an average molecular Weight corresponding to at least 3 and not over 5 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and formaldehyde; said resin being formed in a substantial absence of trifunctional phenols; said phenol being of the formula ,n which R is a para-substituted aliphatic hydrocarbon radical having at least 4 and not more than 14 carbon atoms and substituted in the 2,4,6 position; (b) a basic hydroxylated secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom, and (0) formaldehyde; said condensation reaction being conducted at a temperature above the boiling point of water and belowd 150 C., with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehyde derived methylene bridge connecting the amino nitrogen atom with a resin molecule; with the added proviso that the ratio of reactants be approximately 1, 2 and 2, respectively; with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-Snsceptible; followed by an oxyalkylation step by means of an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide.

9. The process of claim 1 with the proviso that the hydrophile properties of the oxyalkylated condensation reaction employed in the form of a member of the class consisting of (a) the anhydro base as is, (b) the free base, and (c) the salt of hydroxy acetic acid, in an equal weight of xylene are sufi'icient to produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes of Water.

10. The process of breaking petroleum emulsions as defined in claim 1 wherein the oxyalkylation step of the manufacturing process is limited to the use of both ethylene oxide and propylene oxide in combination.

11. The process of claim 10 with the proviso that the hydrophile properties of the oxyalkylated condensation reaction employed in the form of a member of the class consisting of (a) the anhydro base as is, (b) the free base, and (c) the salt of hydroxy acetic acid, in an equal weight of xylene are sufficient to produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes of water.

12. The process of claim 2 with the proviso that the hydrophile properties of the oxyalkylated condensation reaction employed in the form of a member of the class consisting of (a) the anhydro base as is, (b) the free base, and (c) the salt of hydroxy acetic acid, in an equal weight of xylene are sutficient to produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes of water.

'13. The process of breaking petroleum emulsions as defined in claim 2 wherein the oxyalkylation step of the manufacturing process is limited to the use of both ethylene oxide and propylene oxide in combination.

14. The process of claim 13 with the proviso that the hydrophile properties of the oxyalkylated condensation reaction employed in the form of a member of the class consisting of (a) the anhydro base as is, (b) the free base, and (c) the salt of hydroxy acetic acid, in an equal weight of xylene are sufiicient to produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes of water.

15. The process of claim 3 with the proviso that the hydrophile properties of the oxyalkylated condensation reaction employed in the form of a member of the class consisting of (a) the anhydro base as is, (b) the free base, and (c) the salt of hydroxy acetic acid, in an equal weight of xylene are suflicient to produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes of water.

16. The process of breaking petroleum emulsions as defined in claim 3 wherein the oxyalkylation step of the manufacturing process is limited to the use of both ethylene oxide and propylene oxide in combination.

17. The process of claim 16 with the proviso that the hydrophile properties of the oxyalkylated condensation reaction employed in the form of a member of the class consisting of (a) the anhydro base as is, (b) the free base, and (c) the salt of hydroxy acetic acid, in an equal weight of xylene are sufficient to produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes of water.

18. The process of claim 4 with the proviso that the hydrophile properties of the oxyalkylated condensation reaction employed in the form of a member of the class consisting of (a) the anhydro base as is, (b) the free base, and (c) the salt of hydroxy acetic acid, in an equal weight of xylene are sufiicient to produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes water.

19. The process of breaking petroleum emulsions as defined in claim 4 wherein the oxyalkylation step of the manufacturing process is limited to the use of both ethylene oxide and propylene oxide in combination.

20. The process of claim 19 with the proviso that the hydrophile properties of the oxyalkylated condensation reaction employed in the form of a member of the class consisting of (a) the anhydro base as it, (b) the free base, and (c) the salt of hydroxy acetic acid, in an equal weight of xylene are sufiicient to produce an emulsion when said xylene solution is shaken vigorously with l to 3 volumes of water.

21. The process of claim 5 with the proviso that the hydrophile properties of the oxyalkylated condensation reaction employed in the form of a member of the class consisting of (a) the anhydro base as it, (b) the free base, and (c) the salt of hydroxy acetic acid, in an equal weight of xylene are suflicient to produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes of water.

22. The process of breaking petroleum emulsions as defined in claim 5 wherein the oxyalkylation step of the manufacturing process is limited to the use of both ethylene oxide and propylene oxide in combination.

23. The process of claim'22 with the proviso that the hydrophile properties of the oxyalkylated condensation reaction employed in the form of a member of the class consisting of (a) the anhydro base as is, (b) the free base, and (c) the salt of hydroxy acetic acid, in an equal weight of xylene are sufficient to produce an emulsion when said xylene solution is shaken vigorously with l to 3 volumes of water.

24. The process of claim 6 with the proviso that the hydrophile properties of the oxyalkylated condensation reaction employed in the form of a member of the class consisting of (a) the anhydro base as is, (b) the free base, and (c) the salt of hydroxy acetic acid, in an equal weight of xylene are sufficient to produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes of water.

25. The process of breaking petroleum emulsions as defined in claim 6 wherein the oxyalkylation step of the manufacturing process is limited to the use of both ethylene oxide and propylene oxide in combination.

26. The process of claim 25 with the proviso that the hydrophile properties of the oxyalkylated condensation reaction employed in the form of a member of the class consisting of (a) the anhydro base as is, (b) the free base, and (c) the salt of hydroxy acetic acid, in an equal weight of xylene are sufiicient to produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes of water.

27. The process of claim 7 with the proviso that the hydrophile properties of the oxyalkylated condensation reaction employed in the form of a member of the class consisting of (a) the anhydro base as is, (b) the free base, and (c) the salt of hydroxy acetic acid, in an equal weight of xylene are sufiicient to produce an emulsion when said xylene solution is shaken vigorously with l to 3 volumes of water.

28. The process of breaking petroleum emulsions as defined in claim 7 wherein the oxyalkylation step of the manufacturing process is limited to the use of both ethylene oxide and propylene oxide in combination.

29. The process of claim 28 with the proviso that the hydrophile properties of the oxyalkylated condensation reaction employed in the form of a member of the class consisting of (a) the anhydro base as is, (b) the free base, and (c) the salt of hydroxy'acetic acid, in an equal weight of xylene are sufficient to produce an emulsion when said xylene solution is shaken vigorously with l to 3 volumes of water.

30. The process of claim 8 with the proviso that the hydrophile properties of the oxyalkylated condensation reaction employed in the form of a member of the class consisting of (a) the anhydro base as is, (b) the free base, and (c) the salt of hydroxy acetic acid, in an equal weight of xylene are suflicient to produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes of water.

31. The process of breaking petroleum emulsions as defined in claim 8 wherein the oxyalkylation step of the manufacturing process is limited to the use of both ethylene oxide and propylene oxide in combination.

References Cited in the file of this patent Number 5 2,031,557 2,499,365 2,499,368 2,542,011

UNITED STATES PATENTS Name Date Bruson Feb. 18, 1936 De Groote et al. Mar. 7, 1950 De Groote et al. Mar. 7, 1950 De Groote et al. Feb. 20, 

1. A PROCESS FOR BREAKING PETROLEUM EMULSION OF THE WATER-IN-OIL TYPE CHARACTERIZED BY SUBJECTING THE EMULSION TO THE ACTION OF A DEMULSIFIER INCLUDING THE PRODUCTS OBTAINED IN THE PROCESS OF FIRST CONDENSING (A) AN OXYALKYLATION-SUSCEPTIBLE, FUSIBLE, NON-OXYGENATED ORGANIC SOLVENT-SOLUBLE, WATER-INSOLUBLE, LOWER-STAGE PHENOL-ALDEHYDE RESIN HAVING AN AVERAGE MOLECULAR WEIGHT CORRESPONDING TO AT LEAST 3 AND NOT OVER 6 PHENOLIC NUCLEI PER RESIN MOLECULE; SAID RESIN BEING DIFUNCTIONAL ONLY IN REGARD TO METHYLOL-FORMING REACTIVITY; SAID RESIN BEING DERIVED BY REACTION BETWEEN A DIFUNCTIONAL MONOHYDRIC PHENOL AND AN ALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND REACTIVE TOWARD SAID PHENOL; SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCE OF TRIFUNCTIONAL PHENOLS; SAID PHENOL BEING OF THE FORMULA 